CN103140577A - Method for preparing lubricating base oils by using vacuum distilled deasphalted oil - Google Patents
Method for preparing lubricating base oils by using vacuum distilled deasphalted oil Download PDFInfo
- Publication number
- CN103140577A CN103140577A CN2011800380908A CN201180038090A CN103140577A CN 103140577 A CN103140577 A CN 103140577A CN 2011800380908 A CN2011800380908 A CN 2011800380908A CN 201180038090 A CN201180038090 A CN 201180038090A CN 103140577 A CN103140577 A CN 103140577A
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- China
- Prior art keywords
- oil
- deasphalted oil
- heavy
- family
- carried out
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003921 oil Substances 0.000 title claims abstract description 138
- 238000000034 method Methods 0.000 title claims abstract description 118
- 239000002199 base oil Substances 0.000 title claims abstract description 72
- 230000001050 lubricating effect Effects 0.000 title abstract 5
- 239000002904 solvent Substances 0.000 claims abstract description 26
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 24
- 239000004519 grease Substances 0.000 claims description 53
- 238000006243 chemical reaction Methods 0.000 claims description 52
- 238000004821 distillation Methods 0.000 claims description 43
- 239000000314 lubricant Substances 0.000 claims description 34
- 239000003054 catalyst Substances 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 239000002283 diesel fuel Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 230000006837 decompression Effects 0.000 claims description 14
- 238000005194 fractionation Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 238000005292 vacuum distillation Methods 0.000 claims description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 230000000737 periodic effect Effects 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 239000003209 petroleum derivative Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims 4
- 239000000969 carrier Substances 0.000 claims 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 description 25
- 230000003197 catalytic effect Effects 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000012535 impurity Substances 0.000 description 14
- 239000010687 lubricating oil Substances 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000005864 Sulphur Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000004517 catalytic hydrocracking Methods 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 6
- 238000006317 isomerization reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- 229910003296 Ni-Mo Inorganic materials 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical group CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 241000269350 Anura Species 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000305071 Enterobacterales Species 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- -1 SAPO-11 Chemical compound 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
- C10G67/0454—Solvent desasphalting
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C10G59/06—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha plural parallel stages only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
- C10G65/043—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a change in the structural skeleton
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
- C10G67/0454—Solvent desasphalting
- C10G67/0463—The hydrotreatment being a hydrorefining
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
- C10M101/02—Petroleum fractions
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1074—Vacuum distillates
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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- C10G2300/1077—Vacuum residues
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
- C10G2300/206—Asphaltenes
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/302—Viscosity
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2070/00—Specific manufacturing methods for lubricant compositions
Abstract
The present invention relates to a method for preparing lubricating base oils by using vacuum distilled deasphalted oil, and more specifically, to a method for preparing various kinds of lubricating base oils by distilling a distillate obtained from a solvent deasphalting (SDA) process to obtain heavy deasphalted oil (H-DAO) and light deasphalted oil (Lt-DAO), and treating the H-DAO by catalytic reaction and the Lt-DAO by hydrogenation, respectively. According to the present invention, it is possible to obtain a heavy lubricating base oil (150BS) of a high viscosity grade which could not obtained by a known catalytic reaction and a lubricating base oil of group III by hydrogenation, at a high yield, and thus economical efficiency and efficiency are excellent.
Description
Technical field
The present invention relates to utilize the method for preparing high-quality lubricant base and heavy grease base oil through the deasphalted oil of underpressure distillation.
Background technology
The heavy grease base oil of conventional viscosity grade (as the I class: 500N, 150BS etc.) normally makes as follows: long residuum and/or vacuum residuum are introduced the deasphalted oil (DAO) of solvent deasphalting (SDA) device to obtain wherein to have removed pitch and impurity, then solvent extraction is carried out in described deasphalted oil (DAO).
Yet the problem of the heavy grease base oil that makes like this is: because their aromaticity content is high, therefore do not have enough stability, can not satisfy more and more stricter in recent years polycyclic aromatic hydrocarbons (PCA) content standard simultaneously.In addition, being problematic in that of these heavy grease base oils: make because it uses solvent extraction, so its productive rate low (being typically about 40% to 50%), the quantity discharged of environmental pollutant is large, and needs extra additional processing to satisfy PCA content standard (less than 3%).
Therefore, due to people recognize widely exist environmental disruption and economical efficiency poor, so the quantity of utilizing in recent years solvent extraction to prepare the factory of I class lubricating oil base oil reduces.
Yet, because the heavy grease base oil with the specific end use in the fields such as paraffin oil (paraffinic process oil), therefore increases their demand with oil, technique day by day at motor oil, fiber.Therefore, supply falls short of demand for present heavy grease base oil.
Therefore, be devoted at present the standby heavy grease base oil of research and utilization catalyzed reaction legal system.Yet, owing to using ordinary method to be difficult to obtain such as high viscosity heavy grease base oils such as 150BS, therefore use the single reaction method to be not enough to obtain heavy grease base oil from the paramount range of viscosities of low viscosity.Therefore, need to prepare eco-friendly high-quality heavy grease base oil with high yield.
Summary of the invention
Technical problem
Therefore, in order to address the above problem, the inventor has carried out effort.Result, the inventor finds when under the existence of catalyzer, make by when deriving from deasphalted oil (DAO) that solvent deasphalting (SDA) processes and carry out heavy deasphalted oil (H-DAO) experience catalytic reaction process that underpressure distillation obtains, can high yield obtain the heavy grease base oil (as 500N, 150BS etc.) of viscosity grade.In addition, the present invention also finds when using, lightweight deasphalted oil (Lt-DAO) to be carried out that hydrocracking is processed and during the unconverted oil (UCO) that produces, can make the high-quality heavy grease base oil that comprises III class lubricating oil base oil, wherein said lightweight deasphalted oil (Lt-DAO) obtains by underpressure distillation is carried out in deasphalted oil (DAO).
Therefore, the object of the present invention is to provide and a kind ofly prepare high viscosity heavy grease base oil with high yield (grade: the catalyzed reaction method that method 150BS), this high viscosity heavy grease base oil are difficult to by routine obtains.
Another object of the present invention is to provide a kind of method for preparing the high-quality heavy grease base oil that comprises the III class lubricating oil.
Technical scheme
To achieve these goals, one aspect of the present invention provides a kind of utilization to prepare the method for heavy grease base oil through the deasphalted oil of underpressure distillation, the method comprises the following steps: (a) introduce the mixture of long residuum or long residuum and vacuum residuum in solvent deasphalting unit, thereby obtain not wrap bitumeniferous deasphalted oil; (b) underpressure distillation is carried out in described deasphalted oil, thereby obtained lightweight deasphalted oil and heavy deasphalted oil; (c) under the existence of hydrogenation catalyst, hydrotreatment is carried out in the heavy deasphalted oil that obtains in described step (b); (d) under the existence of dewaxing catalyst, the described fraction through hydrotreatment (oil) that obtains in described step (c) is dewaxed; And (e) under the existence of Hydrobon catalyst, the described fraction (oil) through dewaxing that obtains in described step (d) is carried out hydrofining.
Another aspect of the present invention is to provide a kind of utilization to prepare the method for heavy grease base oil through the deasphalted oil of underpressure distillation, comprise the following steps: (a) ' introduce the mixture of long residuum or long residuum and vacuum residuum in solvent deasphalting unit, thus obtain deasphalted oil; (b) ' underpressure distillation is carried out in described deasphalted oil, thereby obtained lightweight deasphalted oil and heavy deasphalted oil; (c) ' with described step (b) ' thus the middle described lightweight deasphalted oil that obtains mixes the preparation mixture with decompression diesel oil, then described mixture is carried out hydrotreatment and fractionation, thereby be petroleum products and unconverted oil with described mixture separation; And (d) ' with described step (c) ' the middle described unconverted oil that obtains is introduced in vacuum distillation process, thus the lubricant base that acquisition has the predetermined viscosity grade.
Beneficial effect
According to the present invention, when will be when deasphalted oil being carried out heavy deasphalted oil that underpressure distillation obtains and introduce in catalytic reaction process, can obtain the high viscosity heavy grease base oil (grade: 150BS) that can not obtain in conventional catalytic reaction process with high yield.In addition, when will when deasphalted oil being carried out lightweight deasphalted oil that underpressure distillation obtains and introduce in catalytic reaction process, preparing the high-quality heavy grease base oil that comprises the III class lubricating oil.In addition, can control by adjusting air distillation residual oil and the ratio of underpressure distillation residual oil, the separation condition of underpressure distillation etc. grade and the productive rate of final lubricant base, thus suitably in satisfying the market to the demand of lubricant base and the continuous variation of supply.
Description of drawings
Fig. 1 illustrates the block diagram that the present invention prepares the process of heavy grease base oil, be separated into heavy deasphalted oil (H-DAO) to process the deasphalted oil (DAO) that obtains by solvent deasphalting (SDA) through the underpressure distillation processing, then hydrotreatment (HDT), catalytic dewaxing (CDW) and hydrofining (HDF) are carried out in described heavy deasphalted oil (H-DAO) successively, prepared thus the heavy grease base oil.
Fig. 2 illustrates the block diagram that the present invention prepares the process of the high-quality heavy grease base oil that comprises III class lubricating oil base oil, wherein, process and to be separated into lightweight deasphalted oil (Lt-DAO) through the deasphalted oil (DAO) that solvent deasphalting (SDA) processing obtains by underpressure distillation, then carry out hydrotreatment (R3), prepare thus the high-quality heavy grease base oil of III class.
[reference number]
AR: long residuum
VR: vacuum residuum
SDA: solvent deasphalting is processed
V1/V1'/V2: underpressure distillation is processed
DAO: deasphalted oil
Lt-DAO: lightweight deasphalted oil
H-DAO: heavy deasphalted oil
R1(HDT): the hydrotreatment reaction
R2: Hydrodewaxing is processed (HDW)/hydrofining and is processed (HDF)
VDU: underpressure distillation is processed
VGO: decompression diesel oil
R3: hydrotreatment
FS: fractionation
UCO: unconverted oil
Implement best mode of the present invention
The below will describe the present invention.
As depicted in figs. 1 and 2, the method for preparing the heavy grease base oil of the present invention comprises the following steps: introduce hydrocarbon raw material in solvent deasphalting unit, thereby obtain the deasphalted oil that asphalt content reduces; And underpressure distillation is carried out in described deasphalted oil, thereby obtained lightweight deasphalted oil and heavy deasphalted oil.
In the present invention, the hydrocarbon raw material that is introduced in solvent deasphalting unit refers to such fraction, it comprises a large amount of heteroatomic compounds and aromatics, and its boiling point is higher than the boiling point of gasoline, such as mixture (AR/VR) of vacuum residuum (VR), long residuum and vacuum residuum etc.Can obtain vacuum residuum by directly crude oil being carried out underpressure distillation, perhaps by distill to obtain vacuum residuum to separating from atmospheric distillation tower the long residuum that obtains under reduced pressure.
Hydrocarbon raw material is introduced solvent deasphalting to be processed in (SDA), to remove pitch and the impurity in hydrocarbon raw material.As the solvent that is used for solvent deasphalting processing (SDA), usually use n-paraffin kind solvent or the isoparaffin kind solvent with 3 to 6 carbon atoms.Particularly, this solvent is selected from n-propane, normal butane, iso-butylene, Skellysolve A and normal hexane.In addition, changed according to the different of operational condition and solvent species from the productive rate of mixture (AR/VR) the preparation deasphalted oil (DAO) of vacuum residuum by vacuum residuum (VR) or long residuum.That is, this productive rate improves along with the increase of the carbonatoms of solvent, and is generally 15% to 80%.
Process by solvent deasphalting the deasphalted oil that (SDA) prepare and comprise metal and the carbon residue of small amount, but have a large amount of aromatic hydrocarbons and have the fraction of high distillation point.Deasphalted oil can directly as prepare the raw material of heavy grease base oil by following catalytic reaction process, perhaps can be used as the raw material for preparing the high-quality heavy grease base oil that comprises III class lubricating oil base oil by following hydrogenation process.Yet, in the present invention, for grade and the productive rate (or ratio) of controlling aptly final lubricant base, and in order to be difficult to the lubricant base by the technology acquisition of routine with the high yield preparation, the present invention carries out underpressure distillation to deasphalted oil, thereby be separated into lightweight deasphalted oil and heavy deasphalted oil, then this lightweight deasphalted oil and heavy deasphalted oil be used separately as the raw material of catalytic reaction process and hydrogenation process.
According to viscosity grade and the productive rate of the target product that will obtain, can control the operational condition that (V1 or V1') processed in underpressure distillation by variety of way.Preferably, carry out under the following conditions underpressure distillation and process (V1 or V1'): column bottom temperature is that 350 ℃ to 430 ℃, tower bottom pressure are that 140mm Hg to 160mm Hg, tower top temperature are that 75 ℃ to 95 ℃, tower top pressure are 60mmHg to 80mmHg.
The character of the character of deasphalted oil (DAO) and lightweight deasphalted oil (Lt-DAO) and heavy deasphalted oil (H-DAO) is shown in following table 1, wherein said deasphalted oil (H-DAO) is by long residuum (AR) and vacuum residuum (VR) are mixed with the ratio of 1:1, then carry out solvent deasphalting to process (SDA) and obtain, described lightweight deasphalted oil (Lt-DAO) and heavy deasphalted oil (H-DAO) obtain by described mixture is carried out underpressure distillation.
[table 1]
Ginseng sees the above table the boiling point distribution of 1 shown deasphalted oil (full cut DAO) and heavy deasphalted oil (H-DAO), can find out that the distribution of heavy deasphalted oil is wide.Therefore, when using deasphalted oil (full cut DAO) when carrying out hydrotreatment reaction, catalytic dewaxing reaction and hydrofining reaction as raw material, can obtain high viscosity heavy grease base oil and moderately viscous II class lubricating oil base oil (viscosity grade: 60N to 150N).Especially, consider the market requirement and product slate, when (can be by underpressure distillation be carried out in deasphalted oil (full cut DAO) with heavy deasphalted oil (H-DAO), with from wherein isolating lightweight deasphalted oil (Lt-DAO), thereby obtaining heavy deasphalted oil at the bottom of tower) when being used as raw material, can be with the heavy grease base oil of high yield preparation corresponding to 500N and 150BS.That is, when using the deasphalted oil through underpressure distillation of the present invention, can obtain to be difficult to the heavy grease base oil that the catalytic reaction process by routine obtains with high yield.
Simultaneously, because the lightweight deasphalted oil (Lt-DAO) shown in table 1 has high paraffinicity and high viscosity index (HVI), therefore when this lightweight deasphalted oil (Lt-DAO) being mixed with decompression diesel oil (VGO) and introduces hydrogenation process, the character of the unconverted oil that produces in this process (UCO) improves, and therefore can prepare the high-quality lubricant base that comprises III class lubricating oil base oil.Especially, the deasphalted oil that (SDA) make (full cut DAO) is different from processing by solvent deasphalting, due to lightweight deasphalted oil (Lt-DAO) aspect impurity (sulphur, nitrogen, breeze) to the decompression diesel oil (VGO) similar, and contain less heavy fraction, therefore it can be mixed with the diesel oil (VGO) that reduces pressure and do not limit its content, and used (in the situation as deasphalted oil (full cut DAO), its blending ratio is restricted to 40% or lower, and uses).
The below will describe the method by preparing the lubricant base with required quality through deasphalted oil introducing catalytic reaction process (R1 and R2) and the hydrogenation process (R3) of underpressure distillation of the present invention in detail.
Consider that the heavy grease base oil comprises the nitrogen of the sulphur of 0.1 % by weight to 0.15 % by weight, 500ppm to 1000ppm and the aromatic hydrocarbons of 10 % by weight to 20 % by weight usually, therefore compare with common heavy grease base oil, the deasphalted oil shown in upper table 1 (DAO) and heavy deasphalted oil (H-DAO) comprise very impurity and the aromatic hydrocarbons of high-content.Therefore, when carrying out catalyzed reaction, the heavy grease feed of base oil can be converted into the product with required quality.
In catalytic reaction process of the present invention, used hydrogenation catalyst, dewaxing catalyst and Hydrobon catalyst, and carried out the hydrotreatment reaction successively, catalytic dewaxing reaction and hydrofining reaction.In each reactions steps that consists of this catalytic reaction process, determine the volume ratio of temperature of reaction, reaction pressure, catalyst type, liquid hourly space velocity (LHSV) and hydrogen and raw material according to the purpose of each reactions steps.
At first, under the existence of hydrogenation catalyst, by heavy deasphalted oil being carried out hydrotreatment process (HDT), thereby remove from raw material such as sulphur, nitrogen, metal, PCA(polycyclic aromatic hydrocarbons) etc. impurity, by hydrogenation is saturated, aromatic component contained in heavy deasphalted oil is converted into the cycloalkanes component simultaneously.The hydrotreatment process is used to adjust the ratio of paraffinic hydrocarbons, naphthenic hydrocarbon and aromatic hydrocarbons, thereby improves the quality of lube base oil production, and is used to remove impurity, thereby obtains high-quality lubricant base.Especially, the main purpose of hydrotreatment process is: remove in might dewax in the downstream (or isomerization) and unifining process as the impurity of catalyst poison pest, its content is reached below target value.
Carry out hydrotreatment process (HDT) under such condition: temperature of reaction is 300 ℃ ~ 410 ℃, and reaction pressure is 30kg/cm
2G ~ 220kg/cm
2G, liquid hourly space velocity (LHSV) is 0.1 hour
-1~ 3.0 hours
-1, and the volume ratio of hydrogen and raw material is 500Nm
3/ m
3~ 3,000Nm
3/ m
3, impurity (as sulphur, nitrogen, metal) and dicyclo or polycyclc aromatic compound in can significantly reducing raw material under optimal conditions thus.In this case, if possible, can reduce the harsh degree of hydrotreatment reaction, make as long as impurity does not affect the life-span of catalyzer in downstream procedures, this is very important.Its reason is, along with the raising of the harsh degree of hydrotreatment reaction, the viscosity of reaction product more reduces, and the productive rate of lube base oil production can descend to some extent thus.
In the hydrotreatment process, catalyzer used comprises and is selected from one or more in the periodic table of elements the 6th family, the 9th family and the 10th family's element, can comprise especially being selected from one or more in Co-Mo, Ni-Mo and combination thereof.Yet hydrotreating catalyst is not limited to this, and can not limit kind ground use, as long as it has required effect to promoting that hydrogenation is saturated and remove impurity.
In the fraction through the hydrotreatment reaction, the content of impurity significantly reduces, and has suitable aromaticity content.Usually, consider fraction to the impact of catalyzer used in downstream process, this fraction can comprise 150ppm or lower sulphur (being preferably 100ppm or lower) and 50ppm or lower nitrogen (being preferably 10ppm or lower).
Like this, because the fraction through the hydrotreatment reaction comprises very small amount of impurity, therefore the catalytic hydrodewaxing in downstream reaction (HDW) can be carried out more stable and effectively, thereby the productive rate when making lubricant base prepare high (production loss is few), and selectivity is high, prepares thus high-quality lubricant base.
Under the existence of dewaxing catalyst, the fraction after hydrotreatment is dewaxed.Catalytic dewaxing process of the present invention refers to, by utilizing isomerization or scission reaction to reduce or removing the process that can destroy the n-paraffin of low-temperature performance.Therefore, after the fraction process dewaxing reaction process of hydrotreatment, it has excellent low-temperature performance, has therefore satisfied the pour point index of lubricant base.
Catalytic dewaxing process carries out under such condition: temperature of reaction is 250 ℃ ~ 410 ℃, and reaction pressure is 30kg/cm
2G ~ 200kg/cm
2G, liquid hourly space velocity (LHSV) is 0.1 hour
-1~ 3.0 hours
-1, and the volume ratio of hydrogen and raw material is 150Nm
3/ m
3~ 1000Nm
3/ m
3
Catalytic dewaxing process catalyzer used comprises carrier and the metal that is carried on carrier.Carrier has acidic site, and is selected from molecular sieve, aluminum oxide, silica-alumina.Molecular sieve refers to crystal aluminosilicate (zeolite), SAPO, ALPO etc.This molecular sieve comprises the mesoporous molecular sieve (such as SAPO-11, SAPO-41, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48 etc.) with 10 yuan of oxygen rings and the large pore molecular sieve with 12 yuan of oxygen rings (such as FAU, beta (Beta), MOR etc.).
Metal used in dewaxing catalyst can be for having the metal of hydrogenation activity, and it is selected from the metal of the periodic table of elements the 2nd, 6,8,9 and 10 families.Especially, the 9th and 10 families (being group VIII) metal can comprise Co, Ni, Pt and Pd, and the 6th family (i.e. group vib) metal can comprise Mo and W.
The deasphalted oil (DAO) that is used as raw material in catalytic dewaxing process has relatively high paraffinicity, and this is to process in (SDA) from the extraction tower top at solvent deasphalting to make because of deasphalted oil (DAO).Therefore, the catalyzer (Ni (Co)/Mo (W)) that has a stronger cracking ability can be used as dewaxing catalyst.Yet, when using this catalyzer (Ni (Co)/Mo (W)), the productive rate of lubricant base and viscosity may reduce, thus the isomerization catalyst (the 10th family's metal) that therefore preferred use can improve pour point by the n-paraffin isomery being turned to isoparaffin.
Under the existence of Hydrobon catalyst, to carrying out hydrofining through the fraction of dewaxing.Unifining process is such process: according to the specification of each target product, under the existence of Hydrobon catalyst, remove alkene and polycyclic aromatic hydrocarbons from the dewaxing fraction, thus the stability of assurance; Particularly can finally control the process of aromatics composition and gas specific absorption when the preparation naphthenic base oils.Usually, unifining process carries out under such condition: temperature of reaction is 150 ℃ ~ 300 ℃, and reaction pressure is 30kg/cm
2~ 200kg/cm
2, liquid hourly space velocity (LHSV) is 0.1 hour
-1~ 3 hours
-1, and the volume ratio of hydrogen and fraction is 300Nm
3/ m
3~ 1500Nm
3/ m
3
In unifining process, catalyzer used comprises carrier and the metal that loads on carrier.Described metal comprises at least a metal that is selected from the 6th, 8,9,10 and 11 family's elements and has hydrogenation activity.Preferably, described metal can be selected from the metallic sulfide of Ni-Mo, Co-Mo and Ni-W, and precious metal, for example Pt and Pd.
In addition, as the carrier of used catalyst in unifining process, can use silicon-dioxide, aluminum oxide, silica-alumina, titanium dioxide, zirconium white or zeolite with high surface area.Preferably, can use aluminum oxide or silica-alumina.The effect of carrier is the dispersiveness by the raising metal, thereby improves Hydrogenation.Importantly control the acidic site of carrier, thereby prevent reaction product generation cracking and coking.
Cut through hydrotreatment process (HDT), catalytic dewaxing process (CDW) and unifining process (HDF) can directly be used as the heavy grease base oil.Yet, also can according to its purposes and viscosity grade, use fractionator to carry out fractionation to this cut, to be separated into the heavy grease base oil.Due to cut has been carried out fractionation, can finally obtain to have the lube base oil production of various viscosity grades.Especially, it is for example 500BS of 500cSt ~ 600cSt(that described heavy grease base oil is included in 40 ℃ of lower kinetic viscosities) the heavy grease base oil, so this heavy grease base oil can be used for required field.
In addition, will by to deasphalted oil (DAO) thus carry out lightweight deasphalted oil (Lt-DAO) that pressure distillation obtains at tower top and will mix by the decompression diesel oil (VGO) that hydrogenation process is converted into lightweight and heavy hydrocarbon.
Hydrogenation process (R3) comprises hydrotreatment process and hydrocracking process, and each process to be once being undertaken by pattern or circulation pattern, and can be arranged on according to different modes in a step or two steps.When will reduce pressure diesel oil (VGO) and lightweight deasphalted oil (Lt-DAO) (raw material in hydrogenation process (R3)) mixed, when the amount of decompression diesel oil (VGO) was higher, the output of high-quality lubricant base improved; And when the amount of lightweight deasphalted oil (Lt-DAO) was higher, high-quality lubricant base and the output that comprises the heavy grease base oil of III class lubricating oil base oil improved.In addition, as the lightweight deasphalted oil (Lt-DAO) as the raw material in the present invention, used by the lightweight fraction that underpressure distillation obtains is carried out in deasphalted oil (full cut DAO), therefore the amount of the amount of the impurity in the lightweight fraction and the impurity in decompression diesel oil (VGO) is similar, and the amount of the heavy end (end tail) in lightweight distillation fraction is similar to or a little more than the amount of the heavy end in decompression diesel oil (VGO), therefore decompression diesel oil (VGO) can be mixed with lightweight deasphalted oil (Lt-DAO) and unrestricted.
By a series of fractionation, prepared light hydrocarbons and heavy hydrocarbon are separated into petroleum products (or transforming oil) and unconverted oil (UCO).With isolated unconverted oil (UCO) all or part of introducing secondary vacuum distillation process (V2), thereby can obtain the high-quality lubricant base of III class and III class heavy grease base oil with high yield.The lubricant base that it is 3.0cSt to 11.0cSt that the lubricant base that obtains by method of the present invention can be included in 100 ℃ of lower kinetic viscosities, particularly kinetic viscosity is the lubricant base of 9.0cSt to 11.0cSt, and this lubricant base is difficult to obtain with high yield by the method for routine.In the open No.2003-0073026 of the Korean unexamined patent application that the inventor submits to, thereby disclose, the unconverted oil that obtains by hydrogenation process is carried out method and the operational condition thereof that underpressure distillation prepares lubricant base, by reference mode is incorporated its full content into this paper here.
As shown in Figure 2, according to one embodiment of the invention, lightweight deasphalted oil (Lt-DAO) and decompression diesel oil (VGO) (introducing the raw material of hydrogenation process) are for carrying out to long residuum the product that underpressure distillation obtains.That is to say, by vacuum distillation process (VDU), long residuum (AR) is distilled, to be separated into decompression diesel oil (VGO) and vacuum residuum (VR), process (SDA) and vacuum distillation process (V1 ') by solvent deasphalting vacuum residuum (VR) is separated into heavy deasphalted oil (H-DAO) and lightweight deasphalted oil (Lt-DAO), then the diesel oil (VGO) that will reduce pressure mixes with lightweight deasphalted oil (Lt-DAO), thereby with the raw material of this mixture as introducing hydrogenation process.
In this case, by heavy deasphalted oil (H-DAO) obtain the heavy grease base oil process can with the process conformity that obtains the high-quality lubricant base of III class and III class heavy grease base oil.Like this, when by the deasphalted oil through underpressure distillation of the present invention, two kinds of different processes being integrated each other, can control by adjusting long residuum and the ratio of vacuum residuum and the separation condition of vacuum distillation process etc. grade and the productive rate of final lubricant base.Therefore, the suitably supply and demand of satisfying the market to lubricant base of lubricant base preparation method of the present invention, and can reduce production costs, thereby improve economical efficiency.
Embodiments of the present invention
Below in conjunction with following example, the present invention is described in more detail.Yet scope of the present invention is not limited to these examples.
Embodiment 1: by heavy deasphalted oil (H-DAO) preparation heavy grease base oil
With the raw material of the heavy deasphalted oil (H-DAO) shown in upper table 1 as the hydrotreatment process.Under the existence of the custom catalysts with hydrogenating desulfurization (HDS), hydrodenitrification (HDN) and hydrodemetallation (HDM) (HDM) function, carry out under the following conditions the hydrotreatment process, described condition comprises: temperature of reaction is 350 ℃ ~ 360 ℃, and reaction pressure is 150kg/cm
2G, liquid hourly space velocity (LHSV) is 0.5 hour
-1~ 1.0 hours
-1, and the ratio of hydrogen and oil is 1,000NL/L ~ 1500NL/L, obtains thus to comprise the fraction of 50ppm or lower sulphur and 5ppm or lower nitrogen.
Subsequently, utilize the fraction that is obtained by the hydrotreatment process to carry out catalytic dewaxing process and unifining process.In catalytic dewaxing process, use the Pt/ zeolite as isomerization catalyst; In unifining process, use (pt/pd)/Al
2O
3As catalyzer.Catalytic dewaxing process and unifining process all carry out under the following conditions: reaction pressure is 140kg/cm
2G ~ 150kg/cm
2G, LHSV are 1.0 hours
-1~ 2.0 hours
-1, and the ratio of hydrogen and oil is 400Nm
3/ m
3~ 600Nm
3/ m
3In addition, catalytic dewaxing process carries out under the temperature of reaction of 330 ℃ ~ 360 ℃, and unifining process carries out under the temperature of reaction of 200 ℃ ~ 250 ℃.In catalytic dewaxing process, temperature of reaction is controlled to be makes the pour point of the cut that obtains in this process be-20 ℃ or lower.
Following table 2 shows the result that the character of raw material and character through the reaction product (before fractionation) of hydrotreatment/dewaxing/unifining process are compared.
[table 2]
As above shown in table 2, has 75 ~ 80 high viscosity grade (kinetic viscosities under 40 ℃) due to fraction, therefore all fraction is seen directly as product, but also can fraction be separated into final heavy grease base oil by fractionation process, thereby obtain the product of viscosity grade, for example 500N and 150BS.The character of the final naphthenic lube oil and base oil that separates is shown in following table 3.The productive rate that can determine heavy grease base oil (500N and 150BS) from table 3 is 75% ~ 80%.
[table 3]
Comparative example 1: the cut that process to be obtained by solvent deasphalting (does not experience underpressure distillation
DAO) preparation lubricant base
With the raw material of the deasphalted oil shown in upper table 1 (full cut DAO) as the hydrotreatment process.Under the existence of the custom catalysts with hydrogenating desulfurization (HDS), hydrodenitrification (HDN) and hydrodemetallation (HDM) (HDM) function, carry out under the following conditions the hydrotreatment process, described condition comprises: temperature of reaction is 350 ℃ ~ 360 ℃, and reaction pressure is 150kg/cm
2G, liquid hourly space velocity (LHSV) is 0.5 hour
-1~ 1.0 hours
-1, and the ratio of hydrogen and oil is 1,000NL/L ~ 1500NL/L, obtains thus to comprise the fraction of 50ppm or lower sulphur and 5ppm or lower nitrogen.
Subsequently, utilize the fraction that is obtained by the hydrotreatment process to carry out catalytic dewaxing process and unifining process.In catalytic dewaxing process, the Pt/ zeolite is used as isomerization catalyst; In unifining process, with (pt/pd)/Al
2O
3As catalyzer.Catalytic dewaxing process and unifining process all carry out under the following conditions: reaction pressure is 140kg/cm
2G ~ 150kg/cm
2G, LHSV are 1.0 hours
-1~ 2.0 hours
-1, and the ratio of hydrogen and oil is 400Nm
3/ m
3~ 600Nm
3/ m
3In addition, catalytic dewaxing process carries out under the temperature of reaction of 310 ℃ ~ 340 ℃, and unifining process carries out under the temperature of reaction of 200 ℃ ~ 250 ℃.In catalytic dewaxing process, temperature of reaction is controlled to be makes the pour point of the cut that obtains in this process be-40 ℃ or lower.
Following table 4 shows the result that the character of raw material and character through the reaction product (before fractionation) of hydrotreatment/dewaxing/unifining process are compared.
[table 4]
As above shown in table 4, in view of being approximately 32.5 40 ℃ of lower kinetic viscosities, and be approximately 4.1 100 ℃ of lower kinetic viscosities, can determine that reaction product comprises the lubricant base of the lubricant base of a large amount of low viscosity grade or medium-viscosity grade (when only processing the H-DAO sample, in view of being approximately 75.6 40 ℃ of lower kinetic viscosities, therefore most of reaction product is heavy lubricant base (500N or higher)).According to viscosity grade, whole fractions are separated.As a result, obtained in the product group shown in following table 5.
[table 5]
Can be learnt by upper table 5, the amount of the light lubricating oil that makes or middle matter lubricant base (for example 60/70N, 100N or 150N) is 40% ~ 45%, and the amount of the heavy grease base oil that makes (500N or higher) is relatively low, for being less than or equal to 30%.Therefore, can determine from embodiment 1 and comparative example 1, and not compare through the deasphalted oil of underpressure distillation, when using the heavy deasphalted oil through underpressure distillation of the present invention, can obtain 500N or higher heavy grease base oil with high yield.
Embodiment 2: by the high-quality lubricate oil base of lightweight deasphalted oil (Lt-DAO) preparation III class
Plinth oil and III class heavy grease base oil
Decompression diesel oil (VGO) and lightweight deasphalted oil (Lt-DAO) mixing that will have character shown in following table 6 with the weight ratio of 6:4, thereby raw materials.
[table 6]
In the hydrotreatment reaction process, utilization has hydrotreatment (HDT) catalyzer of hydrodemetallation (HDM) (HDM), hydrogenating desulfurization (HDS), hydrodenitrification (HDN) and hydrogenation decarburization (HDCCR) function, process under the following conditions prepared raw material, thereby the acquisition fraction, wherein said condition is: liquid hourly space velocity (LHSV) is 1.5 hours
-1, temperature of reaction is 370 ℃ ~ 390 ℃, reaction pressure is 15.0MPa, and the ratio of hydrogen and oil is 1,500NL/L.Subsequently, in the hydrocracking reaction process, utilize hydrocracking (HDC) catalyzer, the fraction that will be obtained by the hydrotreatment reaction process is under the following conditions processed together with the unconverted oil (UCO) of recirculation, and wherein said condition is: LHSV is 0.85 hour
-1, temperature of reaction is that 380 ℃ ~ 400 ℃, reaction pressure are 15.0MPa, and the ratio of hydrogen and oil is 1,500NL/L.
After hydrotreatment reaction and hydrocracking reaction, by separator and a series of fractionation process commonly used, reclaiming boiling point from fraction is 360 ℃ or lower diesel oil and clean or white, and has obtained to have the unconverted oil (UCO) of character shown in upper table 6.Then, unconverted oil (UCO) is introduced secondary vacuum distillation process (V2), then carry out under the following conditions underpressure distillation, obtain thus the light ends of 33 volume %, the 100N cut of 28 volume %, the 150N cut of 22 volume %, the 500N cut of 13 volume % and the final residual oil of 4 volume %, wherein said condition is: tower top temperature is 80 ℃ ~ 90 ℃, and tower top pressure is 65mmHg ~ 80mmHg, and column bottom temperature is 350 ℃, and tower bottom pressure is 120mmHg
Wherein, reclaim the cut of 100N, 150N, 250N and 500N as intermediates, and make light ends and final residual oil be recycled to hydrogenation process (R3).As a result, obtained the III class lubricating oil base oil product of the high viscosity index (HVI) of 100N, 150N and 250N grade, and the heavy grease base oil of the high viscosity index (HVI) of 500N grade.
[table 7]
Although for exemplary purpose discloses the preferred embodiments of the invention, but those skilled in the art can understand, within not breaking away from the spirit and scope of the present invention that the claims of enclosing limit, can carry out multiple change, interpolation or replacement to the present invention.
Claims (10)
1. a utilization prepares the method for heavy grease base oil through the deasphalted oil of underpressure distillation, comprises the following steps:
(a) introduce the mixture of long residuum or long residuum and vacuum residuum in solvent deasphalting unit, thereby obtain deasphalted oil;
(b) underpressure distillation is carried out in described deasphalted oil, thereby obtained lightweight deasphalted oil and heavy deasphalted oil;
(c) under the existence of hydrogenation catalyst, hydrotreatment is carried out in the described heavy deasphalted oil that obtains in described step (b), thereby obtained the fraction through hydrotreatment;
(d) under the existence of dewaxing catalyst, the described fraction through hydrotreatment that obtains in described step (c) is dewaxed; And
(e) under the existence of Hydrobon catalyst, the described fraction through dewaxing that obtains in described step (d) is carried out hydrofining.
2. method claimed in claim 1, further comprising the steps of: as (f) according to range of viscosities, the described of acquisition in described step (e) to be carried out fractionation through hydrorefined fraction, thereby obtain the heavy grease base oil.
3. method claimed in claim 1, wherein in described step (c), the hydrotreatment of described heavy deasphalted oil is carried out under the following conditions, and described condition is: temperature of reaction is 300 ℃ to 410 ℃, and reaction pressure is 30kg/cm
2G to 220kg/cm
2G, and liquid hourly space velocity (LHSV) is 0.1 hour
-1To 3.0 hours
-1And described hydrogenation catalyst comprises and is selected from one or more metals in the 6th family and the 8th family's to the 10 family's elements in the periodic table of elements.
4. method claimed in claim 1, wherein in described step (d), described dewaxing is carried out under the following conditions, and described condition is: temperature of reaction is 250 ℃ to 410 ℃, and reaction pressure is 30kg/cm
2G to 200kg/cm
2G, and liquid hourly space velocity (LHSV) is 0.1 hour
-1To 3.0 hours
-1And described dewaxing catalyst comprises one or more carriers that are selected from molecular sieve, aluminum oxide and silica-alumina, and is selected from one or more metals in the 2nd family in the periodic table of elements, the 6th family, the 9th family and the 10th family's element.
5. method claimed in claim 4, wherein said dewaxing catalyst comprises one or more carriers that are selected from SAPO-11, SAPO-41, ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-48, FAU, BETA and MOR, and is selected from one or more metals in platinum, palladium and nickel.
6. method claimed in claim 1, wherein in described step (e), described hydrofining is carried out under the following conditions, and described condition is: temperature of reaction is 150 ℃ to 300 ℃, and reaction pressure is 30kg/cm
2G to 200kg/cm
2G, and liquid hourly space velocity (LHSV) is 0.1 hour
-1To 3.0 hours
-1And described Hydrobon catalyst comprises one or more carriers that are selected from silicon-dioxide, aluminum oxide, silica-alumina, titanium dioxide, zirconium white and zeolite, and is selected from one or more metals in the 6th family in the periodic table of elements, the 8th family, the 9th family, the 10th family and the 11st family's element.
7. method claimed in claim 2, the heavy grease base oil that it is 500cSt to 600cSt that the described heavy grease base oil that wherein obtains in described step (f) is included in 40 ℃ of lower kinetic viscosities.
8. a utilization prepares the method for heavy grease base oil through the deasphalted oil of underpressure distillation, comprises the following steps:
(a) introduce the mixture of long residuum or long residuum and vacuum residuum in solvent deasphalting unit, thereby obtain deasphalted oil;
(b) underpressure distillation is carried out in described deasphalted oil, thereby obtained lightweight deasphalted oil and heavy deasphalted oil;
(c) with described step (b) thus in the described lightweight deasphalted oil that obtains mix with decompression diesel oil and prepare mixture, then described mixture is carried out hydrotreatment and fractionation, thereby is petroleum products and unconverted oil with described mixture separation; And
(d) the described unconverted oil that obtains in described step (c) is introduced in vacuum distillation process, thus the lubricant base that acquisition has the predetermined viscosity grade.
9. method claimed in claim 8, the described decompression diesel oil in the described vacuum residuum in wherein said step (a) and described step (c) obtains by the described long residuum in described step (a) is carried out underpressure distillation respectively.
10. the described method of claim 8 or 9, the lubricant base that it is 9.0cSt to 11.0cSt that the described lubricant base with predetermined viscosity grade that wherein obtains in described step (d) is included in 100 ℃ of lower kinetic viscosities.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020100052689A KR101779605B1 (en) | 2010-06-04 | 2010-06-04 | Method for producing base oil using deasphalt oil from reduced pressure distillation |
| KR10-2010-0052689 | 2010-06-04 | ||
| PCT/KR2011/004074 WO2011152680A2 (en) | 2010-06-04 | 2011-06-03 | Method for preparing lubricating base oils by using vacuum distilled deasphalted oil |
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| CN103140577A true CN103140577A (en) | 2013-06-05 |
| CN103140577B CN103140577B (en) | 2014-04-23 |
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| CN201180038090.8A Active CN103140577B (en) | 2010-06-04 | 2011-06-03 | Method for preparing lubricating base oils by using vacuum distilled deasphalted oil |
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|---|---|
| US (1) | US8834706B2 (en) |
| EP (1) | EP2578668B1 (en) |
| JP (1) | JP5775571B2 (en) |
| KR (1) | KR101779605B1 (en) |
| CN (1) | CN103140577B (en) |
| ES (1) | ES2610955T3 (en) |
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| WO (1) | WO2011152680A2 (en) |
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| CN112574778A (en) * | 2019-09-27 | 2021-03-30 | 中国石油化工股份有限公司 | Inferior oil hydro-upgrading method and system |
| CN112574778B (en) * | 2019-09-27 | 2022-07-15 | 中国石油化工股份有限公司 | Inferior oil hydro-upgrading method and system |
| CN114790403A (en) * | 2022-04-13 | 2022-07-26 | 盘锦北方沥青燃料有限公司 | Production method of heavy lubricating oil base oil |
| CN114790403B (en) * | 2022-04-13 | 2023-11-10 | 盘锦北方沥青燃料有限公司 | Production method of heavy lubricating oil base oil |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103140577B (en) | 2014-04-23 |
| MY169460A (en) | 2019-04-11 |
| US20130105359A1 (en) | 2013-05-02 |
| EP2578668A2 (en) | 2013-04-10 |
| ES2610955T3 (en) | 2017-05-04 |
| JP5775571B2 (en) | 2015-09-09 |
| US8834706B2 (en) | 2014-09-16 |
| EP2578668B1 (en) | 2016-10-12 |
| WO2011152680A2 (en) | 2011-12-08 |
| EP2578668A4 (en) | 2014-07-23 |
| KR101779605B1 (en) | 2017-09-19 |
| JP2013527303A (en) | 2013-06-27 |
| KR20110133130A (en) | 2011-12-12 |
| WO2011152680A3 (en) | 2012-04-19 |
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